Phosphorodithioates



United States Patent 3,267,181 PHUSPHGRUDITHIOATES Ernst Beriger, Allschwil, Switzerland, assignor to Ciba Limited, Basel, Witzerlaud, a company of Switzerland N0 Drawing. Filed Feb, 21, 1961, Ser. No. 90,635

Claims priority, application Switzerland, Feh. 24, 1960,

8 Claims. (Ci. 26tl-943) This invention provides new organic phosphorus compounds of the formula PSR4CON RiO i l 2 in which R and R each represent an alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radical which may contain substituents, and in the case of an alkyl radical it may be interrupted by at least one oxygen atom, R represents an alkyl or alkylaryl radical interrupted by at least one oxygen atom, R rep-resents a hydrogen atom, an alkyl radical or the same radical as R represents, R represents one of the groups CH OH -CH and CH- in in which R represents a lower alkyl radical, and X represents a sulfur or oxygen atom.

The new compounds are valuable agents for combating pests, especially harmful insects and acarides. They are active against the various stages of development, such as eggs, larvae and imagines, and they act as contact and stomach poisons. Especially valuable as insecticides are compounds of the formula in which R and R each represent an alkyl radical containing 1 to 4 carbon atoms, and advantageously a methyl or ethyl radical, R; has the meaning given above, R represents a radical of the formula L Jr CnHZni-l or of the formula in which R, R and X have the meanings given above, and Me represents a cation, especially an alkali metal ion, is condensed with a compound of the formula R 3 HB1R4 C ON\ R2 (IV) in which R R and R have the meanings given above and Hal represents a halogen atom, such as bromine or chlorine.

The compounds of the Formula III used as starting materials are advantageously dialkyl esters of dithio phos- 3,Z7,l8l Patented August 1 6, i966 phoric acid or of thiol-phosphoric acid of which the alkyl radicals contain 1 to 4 carbon atoms and the carbon chain of the alkyl radicals may be interrupted by at least one oxygen atom, or alkali metal salts of these esters.

The compounds of the general Formula IV are amides of monohalogenated monocarboxylic acids. The radical R may be an alkyl or alkyl-aryl radical interrupted by at least one ether-oxygen bridge, and especially a radical of the formula CmHnDO or of the formula Chloracetic acid Z-methoxyethylarnide, Chloracetic acid Z-phenoxyethylamide, Chloracetic acid Zethoxyethylamide, Chloracetic acid 2:2-diethoxyethylamide, Chloracetic acid 2'-methoxy-Z-ethoxyethylamide, ot-Bromopropionic acid methoxyethylamide and p-Brornopropionic acid-methoxyethylamide.

For making the compounds of the invention the reaction components are reacted within a relatively wide temperature range, for example, at O to 110 C. and advantageously about 10 C. to C. It may be advantageous or convenient to use an inert solvent, such as an alcohol or a ketone, for example, acetone, methanol or Water and, if desired, to work in an atmosphere of an inert gas, for example, under nitrogen, and/ or under reduced pressure.

A further advantageous form of the process for making the compounds of the general Formula 1 consists in reacting the starting materials in a two-phase system consisting of Water and an organic solvent, for example, methylene chloride, in which the relative proportions of the two phases may vary Within relatively wide limits.

The compounds of the Formula 1 can also be. made by reacting a compound of the formula in which R, R R and X have the meanings given above,

and R represents a lower alkyl radical, with a compound of the formula acarides and as carriers for the active substances there may be used gaseous, liquid or solid substances. As such objects or materials to be protected or to be used as carriers there may be mentioned, for example, air, especially in rooms, or liquids, for example, the water in ponds, and finally any dead or living substrate, for example, objects in living rooms, cellars, attics or stables, and also pelts, feathers, wool or the like, and living organisms of the plant or animal kingdom in all their various stages of development, provided that they are insensitive to the pest combating agents.

The combating of pests is carried out by the usual methods, for example, by treating the object or material to be protected with the active compound in the form of vapour, for example, as a fumigant, or in the form of a dusting preparation or spraying preparation, for example, a solution or suspension which may be pre pared with water or a suitable organic solvent, for example, alcohol, petroleum, a tar distillate or the like. There may also be used aqueous solutions or aqueous emulsions of organic solvents which contain the active substances, for brushing, spraying or immersion of the objects or materials to be protected.

The spraying or dusting preparations may contain the usual inert fillers or marking agents, for example, kaoline, gypsum or bentonite, or other additions, such as sulfite cellulose waste liquor, cellulose derivatives or the like, and also the usual wetting or adherent agents for improving the wetting capacity and adherence of the preparations. The pest combating preparations may be in powder form, in the form of aqueous dispersions or pastes, or in the form of self-dispersing oils.

The compounds can be used singly in a pest combating preparation or in conjunction with other insecticides or fungicides. The use of such preparations in plant protection is carried out by the usual spraying, pouring dusting or fumigating methods.

The new compounds are distinguished by their surprisingly low toxicity towards warm blooded animals.

The following examples illustrate the invention the parts and percentages being by weight unless otherwise stated and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the liter.

Example 1 A solution of 19.8 parts of the sodium salt of dimethyldithiophosphoric acid in 40 parts by volume of acetone is treated at room temperature With a solution of 16.55 parts of chloroacetic acid methoxypropylamide (melting at 30 to 31 C.) in 20 parts by volume of acetone. The mixture is stirred for 1 hour at room temperature and then for 3 hours longer at 40 to 45 C., the precipitated sodium chloride is filtered off, and the filtrate is evaporated in vacuo at 40 C. The residue is taken up in 50 parts by volume of methylenechloride and washed with 10 parts by volume of water and then with 10 parts by volume of sodium carbonate solution. The solution is dried over sodium sulfate and evaporated in vacuo at 50 C. As residue there are obtained 20.3 parts of a mobile oil of the formula Example 2 22.9 par-ts of the sodium salt of diethyldithiophosphoric acid are reacted with 16.55 parts of chloroacetic acid Found: P, 10.50%.

methoxypropylamide as described in Example 1, to yield 27.8 parts of a crystalline compound of the formula (G2H5O)ZJI.L SCHZO OllT-CsHsO CH3 Melting point: 40 C. Analysis.-Calculated: P, 9.82%

Example 3 19.8 parts of the sodium salt of dimethyldithiophosphoric acid are reacted with 15.15 parts of chloracetic acid methoxyethylamide (melting at 28 to 29 C.) as described in Example 1, to yield 20.1 parts of a compound of the formula Found: P, 10.1%

(CHaO)2] SCHgCOl IC2H40 CH3 Analysis.Calculated: P, 11.34%. Found: P, 11.2%.

Example 4 22.9 parts of the sodium salt of diethyldithiophosphoric acid are reacted with 15.2 parts of chloroacetic methoxyethylamide as described in Example 1, to yield 28.1 parts of a compound of the formula in Example 1, to yield 25.6 parts of a compound of the formula CH (CHQO)2I SCH2COl ICzH40OH; Analysis.-Calculated: P, 10.78%. Found: P, 11.0%.

Example 6 (a) As described in Example 1, 22.9 parts of the sodium salt of diethyldithiophosphoric acid are reacted with 16.55 parts of chloroacetic acid-N-methyl-N-meth oxyethylamide, to yield 30.7 parts of a compound of the formula t i (CzH5O)2PSCH2O ON-C2H4O CH3 Analysis.-Calculated: P, 9.82%. Found: P, 9.8%.

(b) As described in Example 1, 15.2 parts of chloroacetic acid methoxyethylamide are reacted with 19.8 parts of the potassium salt of dimethylthiophosphoric acid, to yield 22.3 parts of a compound of the formula which can be distilled in a high vacuum.

Boiling point: 133-135 C. under a pressure of 0.12 mm. Hg.

Analysis.-Calculated: S, 12.46%. Found: S, 11.9%.

(c) As described in Example 1, 13.8 parts of chloroacetic acid methoxymethylamide (boiling at 8689 C. under a pressure of 0.14 mm. Hg) are parts of the sodium salt of dimethyldithiophosphoric acid by stirring for 28 hours at room temperature, to yield 16.5 parts of a compound of the formula (cl) As described in Example 1, 13.8 parts of chloroacetic acid methoxymethylamide are parts of the sodium salt of diethyldithiophosphoric acid reacted with 19.8

Found: P, 11.6%. V

reacted with 22.9

by being stirred for 28 hours at room temperature, to yield 25.3 parts of a compound of the formula (CzH O)2] SCHzCONHOHzOCHa Analysis.Calculated: P, 10.78%. Found: P, 10.74%.

Example 7 (a) A solution of 21 parts of o-bromopropionic acid methoxyethylamide (melting at 40 to 42 C.) and 19.8

6 Analysis-Calculated: P, 8.57%. Found: P, 7.5%. (o) By reacting chloracetic acid 2 :2 diethoxyethylamide with the sodium salt of dimethyldithiophosphoric acid the compound of the formula Analysis.Calcu1ated: P, 9.35%. Found: P, 9.14%. (d) By reacting chloroacetic acid 2:2 diethoxyethylparts of the sodium salt of dimethyldithiophosphoric acid i with ifi dlefllyldlthlophosphonc acld in 30 parts of Water is stirred for 20 hours at room terne compoun 0 e Ormu a perature. 50 parts by volume of methylenechloride are added and the Water is separated. The methylenechlo- H ride solution is Washed With 10 parts of water and then (C2H5O)2P S CH2CONHCH2CH(O 0211 with 10 parts by volume of saturated sodium bicarbonate solution, dried over sodium sulfate and evaporated Analysls-" calculatedi Found: P, 356%- in vacuo at 40 to 50 C. to yield 21.65 parts of a compound of the formula Example 9 H 1 A solution of 25.8 parts of 0:0-d1ethy1d1th1ophosphoryl (CHEO)2PScH2CHZCON-C2H4 acetic acid methyl ester in parts by volume of ben- Analysis.Calculated: P, 10.78%. Found: P, 10.1%. zene is refluxed at the boil for 3 hours with 8.9 parts of (b) When the indicated salts of the dithiophosphoric methoXy-propylamine. After cooling, the solution is acid esters are reacted as described above, the compounds 25 Washed successively with 5 parts by volume of Water, 5 1 to 8 shown in the following Table I are obtained: parts by volume of 2 N-hydrochloric acid and 5 parts TABLE I Comp. Dithiophosphoric acid Halogen acid amide Condensation product Analysis No. ester 5 CH3 CH3 P calc: 10.78%. H l H l 1? found: 9.6%. 1 (CHs0)2PS-Na Br0H-0 ONHCzH4O CH3 (0Hi0)i1 s-c11ooNH0211io CH CH3 CH3 P ealc: 9.82%. H H i P found: 9.8%. 2 (C2H5O)zPS-Na B1'CHC ONII02H4OCH3 (C2H5O)2PSCHCONHC2H1OCH S S P oalc: 9.24%. H H P found: 9.9%. 3 (0HiO)2P-sNa 01-01120 ONHCzIL-O- (CHQO)2PS-CHZCONHCQH4O P calc: 9. H H P found: 9 42% 4 (CI-I3O)2PSNa c1oH2ooN(oiH4ooHt)i (CH3O)2PSCH2CON(C2HiOCH3);

S S P Cale: 9.76%. H II P found: 9.6%. 5 (CII O)2PSNa OlCH C ONHC2H4OC2H4OCH3 (CHsO)2P-SCHzOONHC2H4OCzHiOCHs S S P calo: 8.97%. II I! P found: 8.69%. 6 (C2H5O)2PS'N3 0101120 ONHC2H40C2HAOCH3 (C2H5O)2PSCHzCONH-CzH4OCzH OCH 7 OHBO S a S 1? calc: 10.28%. H H 1? found: 9.7%. P-SNa 0101120 ONHO2H4O 0H3 PSCH2C ONHC2H40 0H (CH3)2CEO (CH3)2CHO S P calc: 8.62%. II N P found: 8.53%. s (C2H5O)2P-SNa O1CH2C N( i 4 2 )2PSCHzCON(C2H4O CH3) Example 8 by volume of saturated sodium bicarbonate solution. The

Analysis-Calculated: P, 9.08%. Found: P, 8.2%.

In a similar manner there is obtained (b) By reacting chloroacetic acid methoxyethylamide with the potassium salt of bis-methoxyethyl-dithiophos phoric acid the compound of the formula S ll (CHaOC2H O)zPSCHzC ONlElCzH O CH;

benzene is then evaporated in vacuo and the starting material is removed in a high vacuum at 140 C., to leave as residue 10 parts of a compound of the formula which, according to its melting point and analysis, is

. identical with the compound obtained in Example 2.

Melting point: 40 C. Analysis.Calculated: P, 9.82%; N, 4.44%. P, 10.1%; N, 4.2%.

Found:

Example 10 While being thoroughly stirred for 2 hours at 0 C., 23 parts of OzO dirnethyldithiophosphoryl acetic acid methyl ester are treated with 12.7 parts of a solution of 71% strength of methoxyethylamine in Water. The whole is stirred for another 24 hours at 0 C., 50 parts by volume of methylenechloride are then added, whereupon 8 Of broad beans which Were infested with aphids only on the underside of the leaves, only the upper side of the leaves was sprayed with the above-mentioned liquid spray, and after 48 hours the effect on the underside of the leaves was inspected. The results thus obtained are described in Example 3. summarized in the following Table IV:

TABLE IV 00110. of Effect on aphids by diffusion active principle in liquid Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 (a) Ex. 6 (b) Ex. 6 (0) Ex. 6 ((1) Ex. 7 Table p y I Comp. 4

Example 1] What is claimed is:

2 parts each of a condensation product obtained as de scribed in any one of Examples 1 to 8 are mixed with 1 part of a condensation product from 1 molecular proportion of tertiary octylphenol and 8 molecular proportions of ethylene oxide and with 7 parts of isopropanol. The resulting clear solution is suitable for use as a liquid spray concentrate and can be emulsified by being poured into water.

(A) To determine the contact effect on aphids the following experiment was carried out with the use of liquid sprays containing, respectively, 0.08%, 0.04%, 0.02% and 0.01% of active principle.

Broad beans which were strongly infested with aphids were sprayed all over and after 48 hours the effect achieved was examined. When a 100% effect was observed, the plants were infected with fresh aphids and the effect examined after another 48 hours. The results ob tained are summarized in the following Tables II and III.

1. An organic phosphorus compound of the formula wherein R and R each represents a radical selected from the group consisting of an alkyl radical containing at most 8 carbon atoms and a six-membered cyclic radical, R represents a member selected from the group consisting of a radical of the formula in which m, n and p each represents a whole number from 1 to 4 and a radical of the formula in which m and p each represents a whole number from TABLE II Contact effect on aphids after 48 hours Cone. of active principle in liquid ra E E Sp y Ex. 1 Ex. 2 Ex. 3 Ex. 5 Ex. 6a Ex. 61) Ex. Ex. 6d Talle I Tal1e I TEb lJI Comp. 4 Comp. 7 Comp. 8

TABLE III Contact eflect 48 hours after reinfestation Cone. of active principle in liquid E 7 E I ra Sp y Ex. 1 Ex. 2 Ex. 3 Ex. 5 Ex. 6a Ex. 6b Ex. 60 Ex. 6d Table I Tah le I T lfle l Comp. 4 Comp. 7 Comp. 8

For each plant an identifying mark wasused:

+ signifies that no live aphids were left, signifies insufficient or no effect, signifies goodeifect, only few live aphids left.

out with liquid sprays containing, respectively, 0.08%,

0.04%, 0.02% and 0.01% of active principle.

9 in which R represents alkyl radical containing at most 8 carbon atoms.

2. An organic phosphorus compound of the formula in which R and R each represents an alkyl radical containing at most 4 carbon atoms, R and R each represents an alkyl radical containing 2 to 4 carbon atoms which is interrupted by an oxygen atom and n represents a whole number of at the most 2.

3. The compound of the formula (oH30)zi =s-oH2-o0N(o2H40c1192 4. An organic phosphorus compound of the formula wherein R and R each represents an alkyl radical containing at most 4 carbon atoms, R represents an alkyl radical containing 2 to 4 carbon atoms which is interrupted by an oxygen atom, and R represents an alkyl radical containing at the most 4 carbon atoms.

5. An organic phosphorus compound of the formula ll 0 S R4 R2 10 in which R and R each represents an alkyl radical containing at most 4 carbon atoms, R and R each represents an alkyl radical containing 2 to 4 carbon atoms which is interrupted by an oxygen atom, and R represents an alkyl radical containing at most 4 carbon atoms. 6. An organic phosphorus compound of the formula ber of at the most 2.

7. The compound of the formula 8. The compound of the formula References Cited by the Examiner UNITED STATES PATENTS 2,494,283 1/1950 Cassaday et a1. 260-943 2,959,610 11/1960 Young et al. 260943 2,968,591 1/1961 Tracy 16722 3,080,274 3/1963 Legator et a1. 16722 CHARLES B. PARKER, Primary Examiner.

MORRIS LIEBMAN, IRVING MARCUS, LESLIE H.

GASTON, Examiners.

FRANK M. SIKORA, JOSEPH P. BRUST, RICHARD L. RAYMOND, Assistant Examiners. 

1. AN ORGANIC PHOSPHORUS COMPOUND OF THE FORMULA 